The present invention generally relates to mixed olefin polymerization catalysts, processes employing such catalysts, and polymers obtained therefrom. The novel catalysts comprise the combination of (a) a Group 8-10 transition metal complex of a first compound selected from Set 1, (b) either a Group 8-10 transition metal complex of a second compound selected from Set 1 or Set 2, or a Group 4-6 transition metal complex of Set 3 or Set 4, and optionally (c) a compound Y.
Olefin polymers are used in a wide variety of products, from sheathing for wire and cable to film. Olefin polymers are used, for instance, in injection or compression molding applications, in extruded films or sheeting, as extrusion coatings on paper, for example, photographic paper and digital recording paper, and the like. Improvements in catalysts have made it possible to better control polymerization processes and, thus, influence the properties of the bulk material. Increasingly, efforts are being made to tune the physical properties of plastics for lightness, strength, resistance to corrosion, permeability, optical properties, and the like for particular uses. Chain length, polymer branching, and functionality have a significant impact on the physical properties of the polymer. Accordingly, novel catalysts are constantly being sought in attempts to obtain a catalytic process for polymerizing olefins which permits more efficient and better-controlled polymerization of olefins.
Conventional polyolefins are prepared by a variety of polymerization techniques, including homogeneous liquid phase, gas phase, and slurry polymerization. Certain transition metal catalysts, such as those based on titanium compounds (e.g., TiCl3 or TiCl4) in combination with organoaluminum cocatalysts, are used to make linear and linear low-density polyethylenes as well as poly-xcex1-olefins such as polypropylene. These so-called xe2x80x9cZiegler-Nattaxe2x80x9d catalysts are quite sensitive to oxygen and are ineffective for the copolymerization of nonpolar and polar monomers.
Recent advances in non-Ziegler-Natta olefin polymerization catalysis include the following:
L. K. Johnson et al., WO 96/23010, disclose the polymerization of olefins using cationic nickel, palladium, iron, and cobalt complexes containing diimine and bisoxazoline ligands. This document also describes the polymerization of ethylene, acyclic olefins, and/or selected cyclic olefins and optionally selected unsaturated acids or esters such as acrylic acid or alkyl acrylates to provide olefin homopolymers or copolymers.
European Patent Application No. 381,495 describes the polymerization of olefins using palladium and nickel catalysts that contain selected bidentate phosphorous containing ligands.
L. K. Johnson et al., J. Am. Chem. Soc., 1995, 117, 6414, describe the polymerization of olefins such as ethylene, propylene, and 1-hexene using cationic xcex1-diimine-based nickel and palladium complexes. These catalysts are said to polymerize ethylene to high molecular weight branched polyethylene. In addition to ethylene, Pd complexes act as catalysts for the polymerization and copolymerization of olefins and methyl acrylate.
Eastman Chemical Company has recently described in a series of patent applications (WO 98/40374, WO 98/37110, WO 98/47933, and WO 98/40420) several new classes of Group 8-10 transition metal catalysts for the polymerization of olefins. Also described are several new polymer compositions derived from epoxybutene and derivatives thereof.
G. F. Schmidt et al., J. Am. Chem. Soc., 1985, 107, 1443, describe a cobalt(III) cyclopentadienyl catalytic system having the structure [C5Me5(L)CoCH2CH2-xcexc-H]+, which provides for the xe2x80x9clivingxe2x80x9d polymerization of ethylene.
M. Brookhart et al., Macromolecules, 1995, 28, 5378, disclose using such xe2x80x9clivingxe2x80x9d catalysts in the synthesis of end-functionalized polyethylene homopolymers.
U. Klabunde, U.S. Pat. Nos. 4,906,754, 4,716,205, 5,030,606, and 5,175,326, describes the conversion of ethylene to polyethylene using anionic phosphorous, oxygen donors ligated to Ni(II). The polymerization reactions were run between 25 and 100xc2x0 C. with modest yields, producing linear polyethylene having a weight-average molecular weight ranging between 8K and 350K. In addition, Klabunde describes the preparation of copolymers of ethylene and functional group containing monomers.
M. Peuckert et al., Organomet., 1983, 2(5), 594, disclose the oligomerization of ethylene using phosphine/carboxylate donors ligated to Ni(II), which showed modest catalytic activity (0.14 to 1.83 TO/s). The oligomerizations were carried out at 60 to 95xc2x0 C. and 10 to 80 bar ethylene in toluene to produce xcex1-olefins.
R. E. Murray, U.S. Pat. Nos. 4,689,437 and 4,716,138, describes the oligomerization of ethylene using phosphine/sulfonate donors ligated to Ni(II). These complexes show catalyst activities approximately 15 times greater than those reported with phosphine/carboxylate analogs.
W. Keim et al., Angew. Chem. Int. Ed. Eng., 1981, 20,116, and V. M. Mohring et al., Angew. Chem. Int. Ed. Eng., 1985, 24, 1001, disclose the polymerization of ethylene and the oligomerization of xcex1-olefins with aminobis(imino)phosphorane nickel catalysts.
G. Wilke, Angew. Chem. Int. Ed. Eng., 1988, 27, 185, describes a nickel allyl phosphine complex for the polymerization of ethylene.
K. A. O. Starzewski et al., Angew. Chem. Int. Ed. Engl. 1987, 26, 63, and U.S. Pat. No. 4,691,036, describe a series of bis(ylide) nickel complexes, used to polymerize ethylene to provide high molecular weight linear polyethylene.
WO 97/02298 discloses the polymerization of olefins using a variety of neutral N, O, P, or S donor ligands, in combination with a nickel(0) compound and an acid.
Brown et al., WO 97/17380, describe the use of Pd xcex1-diimine catalysts for the polymerization of olefins including ethylene in the presence of air and moisture.
Fink et al., U.S. Pat. No.4,724,273, describe the polymerization of xcex1-olefins using aminobis(imino)phosphorane nickel catalysts and the compositions of the resulting poly(xcex1-olefins).
Recently, Vaughan et al., WO 97/48736, Denton et al., WO 97/48742, and Sugimura et al., WO 97/38024, describe the polymerization of ethylene using silica supported xcex1-diimine nickel catalysts.
Also recently, Canich et al., WO 97/48735, and Mecking, DE 19707236 A1, describe the use of mixed xcex1-diimine catalysts with group IV transition metal catalysts for the polymerization of olefins. Additional recent developments are described by Sugimura et al. in JP 96-84344 and JP 96-84343, by Yorisue et al. in JP 96-70332, by McLain et al. in WO 98/03559, by Weinberg et al. in WO 9803521, and by Matsunaga et al. in WO 97/48737.
Notwithstanding these advances in non-Ziegler-Natta catalysis, there remains a need for efficient and effective Group 8-10 transition metal catalysts for effecting polymerization of olefins. In addition, there is a need for novel methods of polymerizing olefins employing such effective Group 8-10 transition metal catalysts. In particular, there remains a need for Group 8-10 transition metal olefin polymerization catalysts with both improved temperature stability and functional group compatibility. Further, there remains a need for a method of polymerizing olefins utilizing effective Group 8-10 transition metal catalysts in combination with a Lewis acid so as to obtain a catalyst that is more active and more selective.
The present invention relates to a process for the polymerization of olefins, which comprises contacting one or more olefin monomers of the formula LI:
RCHxe2x95x90CHR5xe2x80x83xe2x80x83LI
with a mixed catalyst system comprising (a) a Group 8-10 transition metal complex of a first compound selected from Set 1, (b) either a Group 8-10 transition metal complex of a second compound selected from Set 1 or Set 2, or a Group 4-6 transition metal complex of Set 3 or Set 4, and optionally (c) a compound Y, 
wherein R and R5 each independently represent a hydrogen atom, a hydrocarbyl or a fluoroalkyl, and may be linked to form a cyclic olefin;
R1 and R6 are each independently hydrocarbyl, substituted hydrocarbyl, or silyl;
R7 is hydrocarbyl;
R8, R9, and R10 are each independently a hydrogen atom, hydrocarbyl, or substituted hydrocarbyl; wherein i and j are each independently a whole number from 1 to 5;
R11 is a hydrogen atom, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, or silyl;
R12 and R13 are each independently hydrocarbyl or substituted hydrocarbyl;
E and W are each independently hydrocarbyl, chloride, bromide or iodide;
Z is a hydrogen atom, hydrocarbyl, substituted hydrocarbyl, OR8, NO2, or CF3;
n is 3 or 4;
A and B are each independently a heteroatom connected mono-radical wherein the connected heteroatom is selected from Group 15 or 16, and wherein A and B may be linked by a bridging group;
Q is C-R4, where R4 is hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, or Oxe2x80x94Si(tert-butyl)(CH3)2;
G2 is hydrocarbyl or substituted hydrocarbyl and may comprise a carbocyclic or heterocyclic ring, thereby forming a 5-membered or 6-membered heterocyclic ring comprising G2, V, N, and N;
V is CR14, N, or PR14R15; wherein R14 and R15 are each independently selected from H, hydrocarbyl, substituted hydrocarbyl, silyl and heteroatom connected hydrocarbyl, and wherein R14 and R15 may collectively form a ring with phosphorus; and
Y is selected from the group consisting of a neutral Lewis acid capable of abstracting Exe2x88x92 or Wxe2x88x92 to form a weakly coordinating anion, a cationic Lewis acid whose counterion is a weakly coordinating anion, and a Bronsted acid whose conjugate base is a weakly coordinating anion, provided that when a compound of Set 3 is part of the mixed catalyst system, a compound Y is present, and
provided that when a compound of the formula VI is used, the Group 8-10 transition metal is Fe or Co.
The present invention further relates to new polyolefins that are made by the novel mixed catalyst system described herein. The polyolefins preferably contain long chain branching at greater than 0.1 long chain branches per polymer chain.
The present invention further relates to a mixed catalyst composition, which comprises (a) a Group 8-10 transition metal complex of a first compound selected from Set 1, (b) either a Group 8-10 transition metal complex of a second compound selected from Set 1 or Set 2, or a Group 4-6 transition metal complex of Set 3 or Set 4, and optionally (c) a compound Y, 
wherein R and R5 each independently represent a hydrogen atom, a hydrocarbyl or a fluoroalkyl, and may be linked to form a cyclic olefin;
R1 and R6 are each independently hydrocarbyl, substituted hydrocarbyl, or silyl;
R7 is hydrocarbyl;
R8, R9, and R10 are each independently a hydrogen atom, hydrocarbyl, or substituted hydrocarbyl; wherein i and j are each independently a whole number from 1 to 5;
R11 is a hydrogen atom, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, or silyl;
R12 and R13 are each independently hydrocarbyl or substituted hydrocarbyl;
E and W are each independently hydrocarbyl, chloride, bromide or iodide;
Z is a hydrogen atom, hydrocarbyl, substituted hydrocarbyl, OR8, NO2, or CF3;
n is 3 or 4;
A and B are each independently a heteroatom connected mono-radical wherein the connected heteroatom is selected from Group 15 or 16, and wherein A and B may be linked by a bridging group;
Q is C-R4, where R4 is hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, or Oxe2x80x94Si(tert-butyl)(CH3)2;
G2 is hydrocarbyl or substituted hydrocarbyl and may comprise a carbocyclic or heterocyclic ring, thereby forming a 5-membered or 6-membered heterocyclic ring comprising G2, V, N, and N;
V is CR14, N, or PR14R15; wherein R14 and R15 are each independently selected from H, hydrocarbyl, substituted hydrocarbyl, silyl and heteroatom connected hydrocarbyl, and wherein R14 and R15 may collectively form a ring with phosphorus; and
Y is selected from the group consisting of a neutral Lewis acid capable of abstracting Exe2x88x92 or Wxe2x88x92 to form a weakly coordinating anion, a cationic Lewis acid whose counterion is a weakly coordinating anion, and a Bronsted acid whose conjugate base is a weakly coordinating anion,
provided that when a compound of Set 3 is part of the mixed catalyst system, a compound Y is present, and
provided that when a compound of the formula VI is used, the Group 8-10 transition metal is Fe or Co.